MXPA04012885A - Cationic alkoxyamines and their use in producing nano particles from natural or synthetic clays. - Google Patents

Cationic alkoxyamines and their use in producing nano particles from natural or synthetic clays.

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Publication number
MXPA04012885A
MXPA04012885A MXPA04012885A MXPA04012885A MXPA04012885A MX PA04012885 A MXPA04012885 A MX PA04012885A MX PA04012885 A MXPA04012885 A MX PA04012885A MX PA04012885 A MXPA04012885 A MX PA04012885A MX PA04012885 A MXPA04012885 A MX PA04012885A
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Mexico
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alkyl
group
methyl
hydrogen
ethyl
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MXPA04012885A
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Spanish (es)
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Peter Nesvadba
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Ciba Sc Holding Ag
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Publication of MXPA04012885A publication Critical patent/MXPA04012885A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings

Abstract

The instant invention relates to cationic alkoxyamines, which are useful as polymerization initiators/regulators in a controlled stable free radical polymerization process to produce intercalated and/or exfoliated nanoparticles from natural or synthetic clays. The invention also relates to improved nanocomposites produced by this process and to the use of these nanocomposite compositions as, for example, coatings, sealants, caulks, adhesives and as plastic additives.

Description

CATIONIC ALCOXYAMINS AND THEIR USE TO PRODUCE NANOPARTICLES OF NATURAL OR SYNTHETIC CLAYS FIELD OF THE INVENTION The invention relates to cationic alkoxyamines, which are useful as initiators / regulators of polymerization in a controlled free radical polymerization process to produce interleaved and / or exfoliated nanoparticles of natural or synthetic clays. The invention also relates to improved nanocomposite compositions produced by this process, the use of such nanocomposite compositions as, for example, coatings, sealants, caulks, adhesives and plastic additives.
BACKGROUND OF THE INVENTION One way to improve the polymeric properties is by adding a natural or synthetic clay material to polymers to form composite materials. However, incorporating clays into polymers may not provide a desirable improvement in physical properties, particularly the mechanical and optical properties of the polymer may be adversely affected. Nanocomposite compositions containing finely dispersed natural or synthetic clay with at least partially interleaved and / or exfoliated layers and mixtures of ethylenically unsaturated monomers and / or polymers thereof have so far attracted much interest in recent years. These materials combine the desired effects of the dispersed clay avoiding the negative influence on, for example, the mechanical or optical properties. These compositions, methods for making them and their use in polymers and coatings are described, for example, in WO 02/24759. Polymerization processes are described using montmorillonite clay, acrylate monomers and for example ammonium persulfate as radical initiator. This conventional polymerization process leads to polymers with broad molecular weight distributions and a broad polydispersity index (PD). Y. Sogah et al., J. Am. Chem. Soc. 1999, 121, 1615-1616 describes the synthesis of dispersed nanocomposite compositions by living-in-situ free radical polymerization of styrene using a silicate-bonded initiator. The nitroxyl compound used is a 2,2,6,6-tetramethyl-piperidine-alkoxyamine. Although Sogah et al. has shown the main possibility of preparing nanocomposite compositions by controlled free radical polymerization, they have been limited to styrene, since the known initiators / regulators are not efficient enough to polymerize acrylates or methacrylates with reasonable conversion rates at acceptable temperatures.
SUMMARY OF THE. INVENTION The present invention provides alkoxyamines, which can be attached to natural or synthetic clays by means of a cationic anchoring group and which have a high reactivity towards acrylates, methacrylates, styrene or other monomers, resulting in a controlled molecular weight with a Narrow molecular weight distribution. With these compounds, polymerization leads to high monomer to polymer conversions in short times and at relatively low temperatures. In contrast to conventional radical polymerization, controlled radical polymerization allows the molecular weight of all growing chains to be adjusted almost uniformly to a predetermined length (low polydispersity), resulting in an almost ideal dispersion of the interspersed clay particles and / or exfoliated. The nanocomposite compositions of the present invention can be almost optically transparent, indicating the fine distribution, on a nanometric scale, of the clay. One aspect of the invention is a compound of formula (I) or (II) (Q + X-) P \ (Q + X-) r. { / 3 N-O (i) / (Q + X ") q where Gi and G2 independently represent a tertiary carbon atom to which unsubstituted Ci-Gis or phenyl alkyl groups or alkyl or phenyl substituted with CN, CO Ci-Ci8 alkyl, CO-phenyl, COO Ci-C18 alkyl are attached Or Ci-Cie alkyl, N02, NH Ci-Cie alkyl or N (Ci-Ci8) alkyl or one of Gi and G2 is a secondary carbon atom which is a group -P (O) ( OR22) 2 and the other is as defined above; or Gi and G2 together with the nitrogen atom to which they are attached form a 5- to 8-membered heterocyclic ring or a polycyclic or spirocyclic 5- to 20-membered heterocyclic ring system, which is substituted with 4 C1-C4 alkyl groups or 2 C5-C12 spirocycloalkyl groups in the ortho position to the nitrogen atom and which may be further substituted with one or more Ci-Cie alkyl groups, Cx-i8 alkoxy or = 0; and Which may be interrupted by an additional oxygen or nitrogen atom; with the proviso that at least one of the 4 C 1 -C 4 alkyl groups in the ortho position to the nitrogen atom is an alkyl higher than the methyl; Li, L2 and L4 is a linking group selected from the group consisting of a direct bond, Ri ~ Y or R2-C (0) -Y- where Y is linked to Gi and / or G2; C1-C25 alkylene, C2-C25 alkylene \ 0 interrupted by -0-, -S-, -SO-, -S02-, -R3, c ' , C5-C8 phenylene and cycloalkylene; Y is 0, or NR9 L3 is a group containing at least one carbon atom and therefore the radical • L3- (QX ") derived from the group that is capable of initiating the polymerization of ethylenically unsaturated monomers; Q2 is a bond direct, O, NR5 or NR5R6; Q + is a cationic group selected from the group consisting of where Rx is Ci-C18 alkylene R2 is a direct bond or alkylene of Ci-Cje? R3 is hydrogen or Cj-Cis alkyl, R4 is hydrogen or Ci-Cie alkyl, R5 / R-6 and R7 are each independently of each other hydrogen, Ci-Ci8 alkyl, C3-C12 cycloalkyl, phenyl or phenylalkyl of C7-C9 or C6-C10 heteroaryl which may or may not be substituted by halogen, OH, N02, CN, Ci-alkoxy R5, R6 and R7 together with the nitrogen or phosphorus atom to which they are attached form a monocyclic or polycyclic ring of 3-12, which may contain additional heteroatoms; R8 is hydrogen or C 1 -C 25 alkyl, C 3 -C 25 alkyl interrupted by oxygen, sulfur or by N-R; or C2-C24 alkenyl, Rg is hydrogen, Ci-Cig alkyl, C3-C18 alkenyl, C3-Ci8 alkynyl, phenyl, C7-C9 phenylalkyl, which may or may not be substituted by one or more hydroxy, halogen or C1- alkoxy groups C4; R22 is Ci-Cie alkyl X "is the anion of a Ci-Cie carboxylic acid which may contain more than one group of carboxylic acid, fluorine, chlorine, bromine, iodine, nitrite, nitrate, hydroxide, acetate, sulfate acid, sulfate, Ci-Cie alkoxy sulfate, aromatic or aliphatic sulfonate, carbonate, acid carbonate, perchlorate, chlorate, t-transfluoroborate, borate, phosphate, phosphate, acid phosphate, diacid phosphate or mixtures thereof; and p, q, and r are independently from each other a different number from 0 to 10 and at least one is different from 0. The alkyl having up to 18 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1, 3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1, 1, 3, 3 ~ tetramethylpent ilo, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
The C3-Ci8 alkyl interrupted by oxygen, sulfur or by N-R3 is, for example, CH3-0-CH2CH2-, CH3-S- CH2CH2-, CH3-N (CH3) -CH2CH2-, CH3-O-CH2CH2-O-CH2CH2-, CH3- (0-CH2CH2-) 20-CH2CH2-, CH3- (0-CH2CH2-) 30-CH2CH2- O CH3- (0-CH2CH2-) 40-CH2CH2-. The phenylalkyl of C7-C9 is, for example, benzyl, -methylbenzyl, a, a-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl and α, α-dimethylbenzyl. The Ci-C25 alkylene is a branched or non-branched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. The alkylene of C2-C2s interrupted by -0-, -S-, \ 0 0 0 -SO-, -SO2-, ^ N -R3, _c- r -C-O- '-C-N-, phenylene or C5-C8 cycloalkylene is, for example, -CH2-0-CH2-, -CH2-S-CH2-, -CH2-N (CH3) -CH2-, -CH2-0-CH2CH2-, -CH2CH2- 0- CH2CH2-, -CH2CH2 -0-CH2CH2-0-CH2CH2-, -CH2CH2- (0-CH2CH2-) 20- CH2CH2-, -CH2CH2- (0-CH2CH2-) 30-CH2CH2 -, -CH2CH2- (0 -CH2CH2-) 40- OR CH2CH2 ~, -CH2CH2- S -CH2CH2-, -CH ^ -CH ^ -C-NH- (CH2) -, O -CH CH2-C-NH- (CH2) 6-, -cHg-CHj- ^ "" ^ -CHg-CHg- or -CH ^ -CH ^ V-CH CH-.
The alkenyl having from 2 to 24 carbon atoms is a branched radical or not, such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2- butenyl,? -2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,? -2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having from 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms. The alkynyl having from 3 to 18 carbon atoms is a branched radical or not, for example propynyl, 2-butynyl, 3-butynyl, isobutynyl, n-2,4-pentadiinyl, 3-methyl-2-butynyl,? 2-octynyl,? -2-dodecinyl, isododecinyl. Halogen is, for example, clerical, bromine or iodine.
Preference is given to chlorine and bromine. Alkoxy having up to 25 carbon atoms is a branched or non-branched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having from 1 to 12, especially from 1 to 8, for example from 1 to 6, carbon atoms. The alkanoyloxy having up to 25 carbon atoms is a branched or unbranched radical, for example acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given to the alkanoyloxy having from 2 to 18, especially from 2 to 12, for example from 2 to 6, carbon atoms. The C2-C18 alkyl substituted with hydroxyl is a branched radical or not which preferably contains from 1 to 3, in particular 1 or 2, hydroxyl groups, for example, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexy-1, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7- hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2- hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxy-octadecyl. The C5-C12 cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl or cyclooctyl. If X "is a monovalent radical of a saturated, unsaturated or aromatic carboxylic acid, that is, for example, an acetyl, caproyl, steroyl, acryloyl, methacryloyl, benzoyl or β- (3, 5-di-tert-butyl) radical, 4-hydroxyphenyl) propionyl If X "is a divalent radical of a dicarboxylic acid, this is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl ( 3, 5-di-tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptendicarbonyl. If X "is a trivalent radical of a tricarboxylic acid, this is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.The heteroaryl is for example, pyrile, thiophenyl, furyl, pyridyl or pyrimidyl.When R5, R5 and R7 form a monocyclic or polycyclic heterocyclic ring, the resulting cation is for example a pyridinium, quinolinium, isoquinolinium, imidazolium or thiazolium cation.
DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE INVENTION In one embodiment of the present invention in formula I or II -Li (Q + X ~), -L2 (Q + X ~), and -L3 (Q + X "), are a group where Ki and K2 are hydrogen, C5-C12 cycloalkyl, phenyl or phenylalkyl of C7-C9 K3 is a group -COK4 or // -K where K4 is -Y- [(CH2-CH2) - (CH2) S-N + R5RS X ~] t-CH2-CH2- (CH2) s-N + R5R6R7 X "or -Y-CH2-CHOH-CH2-N + R5R6X "-. { [(CH2-CH2) - (CH2) S-N + X "R5R6] t-CH2-CH2- (CH2) 3-N + R5R6R7 X"} u, where s is a number from 0 to 8, t is a number from 0 to 4 and u is O or 1 and Y e.s -O- or -NR9; or K4 is a group J / X Q X -Y N-R5 X N N X R.
Z is -C (O) - or a direct bond, if Z is -C (0) -, ¾ has the same meaning as ¾, if Z is a direct bond, K5 is Y-CH2-CHOH-CH2-N + R5Re X "- { [(CH2-CH2) - (CH2) S-N + R5RS? T -CH2-CH2- (CH2.} .S-N + R5R6R7X-.}.
Q + X ~, -CH2Q + X "or -CHCH3Q + X" and Y is -0- or -NR9 or a direct bond; the other substituents are as defined above. Preferably the compounds are of the formulas Ib, Ic, Id or you (la) (Ib) (le) (Id) (him) where Qi is a direct link or a group -CH2-; if Qi is a direct bond, Ta is hydrogen, if Qi is -CH2-, Te is methyl or ethyl; Ti, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 and T10 are independently hydrogen or methyl; T5 and T6 are hydrogen or T5 and T6 together are a group = 0, = N0H, = N0-T9 or T5 is hydrogen and T6 is -O-T9 or -NR9-T9 where T9 is hydrogen, R9 or -C (0 ) -R9, wherein R9 is hydrogen, Ci-Cj8 alkyl, C3-Ci8 alkenyl, C3-Ci8 alkynyl, phenyl, C7-C9 phenylalkyl, which may or may not be substituted by one or more hydroxy groups , halogen or C1-C4 alkoxy; ? 12 / · T13, 14, T15 and i6 are independently Ci-Cia alkyl, C3-C13 alkenyl, C3-CiB alkynyl, C5-C12 cycloalkyl, phenyl or C7-C9 phenylalkyl; or u is hydrogen and? 12 is a group -P (O) (OC2H5) 2 and the others are as defined above; o You and 14 are a group -CH2-0-T9 and the others are as defined above; or is is a group -C (0) -Y-R5 and the others are as defined above; or Tu, 12 and 13 are a -CH2OH group; where Ki and K2 are hydrogen, C5-C12 cycloalkyl, phenyl or phenylalkyl of C7-C9 and K3 is a group -COK4 or where K4 is Y- [(CH2-CH2) - (CH2) s -N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 ~ or -Y-CH2-CHOH-CH2-N + R5R6X" - . { [(CH2-CH2) - (CH2) S-N + X "R5R6] t ~ CH2-CH2 -, (CH2) S-N + R5R6R7 X"} u, where s and t is a number from 0 to 4 and u is 0 or 1; or is it a group? Q + X -Y N-R5 X Z is -C (0) - or a direct bond, if Z is -C (0) - K5 has the meaning of K4, if Z is a direct bond, 5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R5 X '] t -CH2-CH2- (CH2) S-N + R5R5R7X"} u, Q + X ~, ~ CH2Q + X ~ or -CHCH3Q + X ~; And it is -0- or -NRg; X "and the other substituents are as defined above In another preferred embodiment of the present invention the compounds are of the formulas lia, Ilb, lie, lid or lie where Ai and A2 are independently hydrogen or together with the carbon atom to which they are attached they form a carbonyl group, -C (0) -; D is a direct bond or alkylene of Ci-C12, alkylene of C1-C12 which is interrupted by one or more 11 atoms of 0, S, or NRg, C5-C12 cycloalkylene or phenylene; E is a group -NR9- (CH2) X-NR9- where x is a number from 2 to 12 or a group v is a number from 0 to 10 and w is 0 or 1; Qi is a direct link or a group -CH2-; if Qi is a direct bond, T8 is hydrogen, if Qi is -CH2-, T8 is hydrogen, methyl or ethyl; And it is -0- or -NR9; Ti, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; -L3 (Q + X ~), is a group where Ki and K2 are hydrogen, C5-Ci2 cycloalkyl, phenyl or phenylalkyl of C7-Cg and K3 is a group -COK4 or ^ ^ Z_K where K4 is Y-t (CH2-CH2) - (CH2) S-N + R5R6 X ~] t-CH2-CH2- (CH2) S-N + R5R6R7 X ~ or -Y-CH2-CHOH-CH2-N + R5R6X_-. { [(CH2-CH2) - (CH2) S-N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 X ~) u, where syt is a number of 0-4 and u is 0 or 1; or K X Z is -C (O) - or a direct bond, if Z is -C (O) - K5 has the meaning of ¾, if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X-] t-CH2-CH2- (CH2) S-N + R5R6R7 X "lu, Q + X", -CH2Q + X ~ or -CHCH3Q + X "; X and the other substituents are as defined above. Compounds of formulas Illa, Illb, IIIc, Illd or lile are also preferred (llld) (lile) Ti, γ2, γ3 and ¾ are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; And it is 0 or NR9; Qi is a direct link or a group -CH2-; if Qi is a direct bond, Ts is hydrogen, if Qi is -CH2-, T8 is methyl or ethyl; v is a number from 0 to 10 and w is 0 or 1; K7 is a group -CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2- (CH2) 3-N + R5R6R7".}. u, where syt is a number of 0-4 and u is 0 or 1, or a group -D] .- Q + X ~ where Di is Ci-Ci2 alkylene, Ci-C12 alkylene which is interrupted by one or more 0, S, or NR9 atoms, Cs-Ci2 cycloalkylene or phenylene; K6 is selected from the group consisting of -CH2-CH2-aryl, l of C5-C6) 2CCN, (C 1 -C 12 alkyl) 2CCN, -CH 2 CH = CH 2, alkyl (Ci-Ci 2) -CR30-C (0) -alkyl (from C1-C12), alkyl (from Ci-C12) -CR30-C (O ) -aryl (of C6-C10), alkyl (of C1-C12) -CR30-C (0) -alkoxy (of C1-C12), alkyl (of C1-C12) -CR30-C (0) -phenoxy, (C1-C12 alkyl) -CR30-C (0) -N-dialkyl (of C1-C12), alkyl (of C1-C12) -CR30-CO-NH alkyl (of C1-C12), alkyl of (from Ci-Ca2) -CR30-CO-NH2, -CH2CH = CH-CH3, -CH2-C (CH3) = CH2, -CH2-CH = CH-phenyl, _Q [_ | _Q ^ -CH, 3-cyclohexenyl, 3 and R30 is hydrogen or C1-C12 alkyl; the alkyl groups are substituted or not with one or more -OH, -COOH or -C (O) R30 groups; and the aryl groups are phenyl or naphthyl which are substituted or unsubstituted with Ci-Ci_2 haloalkyl, C1-C12 alkoxy, C1-C12 alkylcarbonyl, glycidyloxy, OH, -COOH or -COO (C1-C12) alkyl and X "and the other substituents are as defined above, Particularly suitable are the compounds according to formula IVa where Ti, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; Ei is where x is a number from 2 to 12; K ~ 6 is selected from the group consisting of -CH2-CH2-aryl, l of C5-C5) 2CCN, (C 1 -C 12 alkyl) 2CCN, -CH 2 CH = CH 2, (C 1 -C 12 alkyl) -CR 30 -C (0) -alkyl (from ¾-> ¾>, alkyl (from Ci-Ci 2) -CR 30 -C (O) -aryl (of C6-Cio), alkyl (of Ca-C12) -CR20-C (0) -alkoxy (of Ci-Ci2), alkyl (of C1-C12) -CR30-C (0) ) -phenoxy, alkyl (of Ci-C12) -CR30-C (0) -N-dialkyl (of Ci-C12), alkyl (of C1-C12) -CR30-CO-NH alkyl (of C1-C12), alkyl (Ci-C12) -CR30-CO-NH2, -CH2CH = CH-CH3, -CH2-C (CB3) = CH2, ^ Q | _J -CH2-CH = CH-phenyl, _Q | _] JQ ^ > , 3-cyclohexyl, 3 R30 is hydrogen or Ci-Ci2 alkyl; the alkyl groups are substituted or not with one or more -OH, -C00H or -C (O) R30 groups; and the aryl groups are phenyl or naphthyl which are substituted or unsubstituted with Ci-Ci2 alkyl, halogen, di-Ci2 alkoxy, Ci-C12 alkylcarbonyl, glycidyloxy, OH, -COOH or -C00 alkyl (from C1-C12) ) and X "and the other substituents are as defined above.Preference is also given to the compounds of the formulas Va, Vb, Ve, Vd or Ve (Go) (Vb) (Go) (Vd) (Go) where Ti, 2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; Qi is a direct link or a group -CH2-; if Qx is a direct bond, Tg is hydrogen, if Qi is -CH2-, ü is methyl or ethyl; Ki and K2 are hydrogen, C5-C2 cycloalkyl, phenyl or phenylalkyl of C7-C9 and K3 is a. group -COK4 or ^ ^ z. «5 where 'K4 is Y- [(CH2-CH2) - (CH2) s -N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 X" or -Y-CH2-CHOH-CH2-N + R5R6X ~ -. { [(CH2-CH2) - (CH2) s "N + R5R6 X ~] t-CH2-CH2- (CH2) s-N + R5R6R7 X ~ lu, where syt is a number of 0-4 and u is 0 or 1; or ? or Z is -C (O) - or a direct bond, if Z is -C (O) - K5 has the meaning of K4, if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 ?? t -CH2-CH2- (CH2) S- + j and i X_) u, Q + _, -CH2Q + X "or -CHCH3Q + X"; K7 is a group -CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X-] t-CH2-CH2- (CH2) S-N + R5R6R7 '.}. u, where syt is a number of 0-4 and u is 0 or 1, or a group -Di- Q + X- where Di is Ci-C12 alkylene, Ci-Ci2 alkylene which is interrupted by one or more O, S, or NR9 atoms, C5-C12 cycloalkylene or phenylene; X "and the other substituents are as defined above.Compounds of formula Via are also preferred. where Ti, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; Ei is where x is a number from 2 to 12; Ki and K2 are hydrogen, C5-Ci2 cycloalkyl, phenyl or phenylalkyl of C7-C9 and K3 is a group -C0K4 or ^. -Ks where K4 is Y- [(CH2-CH2) - (CH2) S ~ N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 X "or -Y-CH2-CHOH-CH2-N + R5RgX" -. { [(CH2-CH2) - (CH2) S-N + R5R6 X "] t -CH2-CH2- (CH2) S-N + R5R6R7 X"} ", Where s and t are a number of 0-4 and u is 0 or 1; or Z is -C (O) - or a direct bond, if Z is -C (O) - K5 has the meaning of K4r if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2- (CH2) S-N + R5R6R7 X " } u, Q + X ~, -CH2Q + X ~ or -CHCH3Q + X "and X ~ and the other substituents are as defined above.
Ial, Ibl, Icl, Idl or I read (Ia1) (Ib1) (Id) (Id1) (le1) where Qi is a direct link or C¾; i, T3 are ethyl and T2, T4 are methyl; T7 is methyl or H; if Q1 is a direct link, T8 is H; if Qx is CH2, T8 is methyl or ethyl; ío is H if T7 is methyl or Ti0 is methyl if T7 is H; u, 12, 13, Ti 4, T 15 and Ti 6 are independently methyl or ethyl; or u is H, 12 is isopropyl, 13 is phenyl and i4, i5, i6 are methyl; or u is H, T12 is -P (= 0) (OC2H5) 2, T13 is t-butyl and T14, T15, i6 are methyl; c u and 14 are -CH20-Tq and T12 T15 are methyl or phenyl and T13, Ti6 are methyl or ethyl; or u, T12, 13, T14, T15 are methyl and 16 is a group -CO-0-R9 or -CON (R9) 2; or Tu, T12 and T13 are -CH2OH, T14 is H, T15 is isopropyl and i6 phenyl; T9 is hydrogen, R9 or -C (0) -R9, where R9 is hydrogen, Ci-C18 alkyl, C3-Ci8 alkenyl, C3-C18 alkynyl, phenyl, C7-C3 phenylalkyl; Ki is H, K2 is methyl or ethyl and K3 is a group K4 is -Y-CH2-CH2- (CH2) S-N + X ~ R5R6R7 or; -y-CH2-CHOH-CH2-N-CH2-CH2- (CH2) S-N + X "R5R6R7 where Y is O or NR9 and s is a number from 0 to 2; if K3 is ^ 2.- ?? 'z is _co ~ or a direct link; if Z is -C0-, K5 has the same meaning as K4; if Z is a direct bond, K5 is a group -0-CH2-CHOH-CH2-N-CH2-CH2- (CH2) S-N + X_R5R6R7 or -CH2N + R5R6R7 X "and X- and the other substituents are as The compounds of formula Ilal, Ubi, IIcl or Ildl are also of particular interest. where Qi is a direct link or C¾; Ti, T3 are ethyl and T2, T4 and T7 are methyl; if Qi is a direct link, T8 is H; if Qi is CH2, T8 is methyl or ethyl; D is a direct bond, C1-C12 alkylene or phenylene; E is -NR5- (CH2) X -N 5- where x is from 2 to 12 or a group Ki is H, K2 is methyl or ethyl and K3 is a group -CO-K4 or - ^ ^, -?; K4 is -Y-CH2-CH2- (CH2) S-N + X "R5R6R7 or; -Y-CH2-CHOH-CH2- -CH2-CH2- (CH2) where Y is 0 or NRg and s is a number of 0 a 2 if K3 is < ~~ ^% Z-K 'z is _co_ 0 a direct link; if Z is -CO- K5 has the same meaning as K4; if Z is a direct bond K5 is a group -0 ~ CH2-CHOH-CH2-N-CH2-CH2- (CH2) s -N + X "R5R6R7 or -CH2N + R5R6R7 X"; and X "and the other substituents are as defined above The precursors of the above compounds can be prepared according to known methods The preparation of open chain alkoxyamines is described for example in WO 99/03894 or in WO The alkoxyamines based on tetraalkyl piperidine are for example described in GB 2 335 1290 or in GB 2 361 235. Additional heterocyclic alcoxylamines are described in GB 2 342 649. A very suitable method, but not the only one It is possible, for the introduction of the cationic entity to the alkoxyamine molecule, to first prepare the suitable alkoxyamine precursor which is then quaternized Examples of these alkoxyamines are given in the examples in Table 1. The non-cationic precursors can be be prepared by a variety of methods described in the patents cited using suitable construction blockers containing the appropriate nucleophilic groups ca Peace of being cuternized. A few examples of such groups are primary, secondary or tertiary amine groups, pyridyl group, quinolyl, isoquinolyl, imidazolyl, thiazolyl, trialkyl or triaryl groups or alkylarylphosphine or a thioether group. These can be quaternized by a variety of electrophilic reagents, for example alkyl halides, alkyl sulfonates, alkyl carbonates, trialkyloxonium salts, epoxides or others. A special case is the formation of the cationic amount by the protonation of the nucleophilic groups mentioned by their protonation with acids. A given specific anion of the cationic alkoxyamine can be exchanged with a different one using for example ion exchangers or the well-known ionic metathesis. A further aspect of the invention is a process for preparing a monomer / polymeric clay nanocomposite dispersion comprising the steps of A) Providing a first aqueous dispersion of a natural or synthetic clay that can be interspersed and / or partially exfoliated and where the clay has an exchangeable cation; adding a compound according to claim 1 to the dispersion and exchanging the cation at least partially; B) Add the dispersion to at least one ethylenically unsaturated monomer and polymerize at least a portion of the ethylenically unsaturated monomer. Clay minerals are typically comprised of hydrated alumina silicates that are fine-grained and have a luminous habit. The crystalline structure of a typical clay mineral is a multi-layer structure comprised of combinations of tetrahydric SiO4 layers that are bonded to layers of A10 (0H) 2 octahydric. The so-called "gallery" is also formed, which describes the defined interlayer spaces of stratified clay minerals. Depending on the clay mineral the gallery may contain water and / or other constituents such as potassium cations, sodium or calcium. Clay minerals vary based on the combination of their layers and constituent cations. Isomorphic substitution of clay mineral cations, such as Al3 + or Fe3 + that substitute Si4 + ions in the tetrahydric network, or Al3 +, Mg2 + or Fe2 + that substitute other cations in the octahedral network, typically occur and can impart a negative net charge on the structure of clay. The natural elements within the clay gallery, such as water molecules or sodium or potassium cations, are attracted to the surface of the clay layers due to their net charge. Nanocompositions are compositions in which at least one of its constituents has one or more dimensions, such as length, width or thickness in the range of the manometric size. The term nanocomposition, as was done here, denotes the state of matter, where polymer molecules exist between at least partially exfoliated clay layers. The term "interleaved nanocomposition", as used herein, describes a nanocomposition containing a regular insertion between the layers of clay. The term "exfoliated nanocomposition" as used herein describes a nanocomposition where clay layers of 1 nm thickness are dispersed in the matrix (oligomer / polymer) which forms a nano / micro scale composite structure. Clay minerals are commercial products and are distributed, for example, by Süd-Cheraie Inc., Germany. Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinyl imidazole, maleic anhydride, anhydrides of (alkyl) acrylic acid, (alkyl) acyl acid salts, (alkyl) acrylic esters, (meth) acrylonitriles, (alkyl) acrylamides, vinyl halides or vinylidene halides. Particularly ethylenically unsaturated monomers are ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, C5-C13 ot-alkene, styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH2 = C (Ra) - (C = Z) where Ra is hydrogen or C1-C4 alkyl, Rb is NH2, O "(Me +), glycidyl, unsubstituted Ci-Ci8 alkoxy, C2-Cioo alkoxy interrupted by at least one W and / or O atom, or Ci-Cis alkoxy substituted with hydroxy, alkylamino Unsubstituted CX-CIB, di (Ci-Cie alkyl) araino, C1-C18 alkylamino substituted with hydroxy or di (Ci-Ci8 alkyl) amino substituted with hydroxy, -0-CH2-CH2-N (CH3) 2 or -0-CH2-CH2-N + H (CH3) 2 An "; i¾n ~ is an anion of a monovalent organic or inorganic acid; I am a monovalent metal atom or the ammonium ion. Z is oxygen or sulfur. Examples for Ra as C2-C10o alkoxy interrupted by at least one O atom are of formula , wherein Rc is C1-C25 alkyl, phenyl or phenyl substituted by Ci-Ci8 alkyl, Rd is hydrogen or methyl and v is a number from 1 to 50. These monomers are derived, for example, from nonionic surfactants by the acrylation of the corresponding alkoxylated alcohols or phenols. The repeating units can be derived from ethylene oxide, propylene oxide or mixtures of both. Additional examples of suitable acrylate or methacrylate monomers are given below. where An ~ and Ra have the meanings defined above and Re is methyl or benzyl. ?? "is preferably Cl", Br "or" 03S-CH3. The additional acrylate monomers are Examples of suitable monomers other than acrylates Preferably Ra is hydrogen or methyl, Rb is N¾, glycidyl, C 1 -C 4 alkoxy unsubstituted or substituted by hydroxy, unsubstituted C ~ C 4 alkylamino, di (C 1 -C 4 alkyl) amino, Ci-C alkylamino substituted with hydroxy or di (C 1 -C 4 alkyl) amino substituted with hydroxy; and Z is oxygen. Also suitable ethylenically unsaturated monomers are styrene, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tertbutyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate ,. glycidyl acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, di-methylaminoethyl (meth) acrylate, (met ) acrylates of glycidyl, acrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl methacrylamide. The preferred one is a process wherein the ethylenically unsaturated monomer is selected from the group consisting of Ci-Cis alkyl methacrylate, Ci-Ci8 alkyl acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, ( met) lauryl acrylate, allyl (meth) acrylate, stearyl (meth) acrylate, acrylic acid, itaconic acid, methacrylic acid, butadiene, vinyl acetate, vinyl versatate, styrene, (me) hydroxyethyl acrylate, ) hydroxypropyl acrylate, vinyl aromatic monomers, divinylbenzene, divinylpyridine, divinyl toluene, diallyl phthalate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, divinylxylene, divinyl ethylbenzene, divinyl sulfone, divinyl ketone, divinyl sulfide, maleate diallyl, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, divinyl sebacate, diallyl tartrate, dia silicate lilo, triallyl tricarbalylate, triallyl aconite, triallyl citrate, triallyl phosphate,?,? -methylene dimethacrylamide,, N-methylene dimethacrylamide, N, N-ethylenediacrylamide, trivinylbenzene, and the polyvinyl ethers of glycol, glycerol, pentaerythritol, resorcinol, monothio and dithio derivatives of glycols, and combinations thereof. Special preference is given to a process where unsaturated monomer containing acid is added, which is selected from the group consisting of methacrylic anhydride, maleic anhydride, itaconic anhydride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, acid acryloxypropionic, (meth) acryloxy propionic acid, styrene sulfonic acid, ethylene methacrylate-2-sulfonic acid, 2-acrylamido-2-methylpropane, sulfonic acid; phosphoethyl methacrylate; the corresponding salts of the acid-containing monomer, and combinations thereof. In one embodiment of the invention, the process is carried out where the aqueous phase of step A) is removed at least partially before carrying out step B). It is also possible that in step B) an organic solvent is additionally added. The preferred is a process where the polymerization is carried out by applying heat, at a temperature of 60 ° C to 160 ° C. The preferred is a process where the compound of formula I or II is added in an amount of 1% to 100%. % by weight, based on the weight of the clay. Preferably the weight ratio between the ethylenically unsaturated monomer added in step B) and the clay of step A) which is at least partially interspersed with a compound of formula I or II is from 500: 1 to 1: 5. In a specific embodiment of the present invention, the process is carried out where an additional cationic compound selected from the group of cationic surfactants is added in step?). Typical surfactants are amino acids or alkylammonium ions. The amino acid surfactants transfer a proton from the COOH group to the NH2 group forming an NH3 + group which can be exchanged with a cation of the clay mineral. For example the alkylammonium ion is CH3- (CH2) n-NH3 + where n is from 1 to 18. It is believed that the alkylammonium cations are readily exchanged with the natural cations present between the clay platelets resulting in an intercalated state. It is also possible to repeat the process of step B) with a second ethylenically unsaturated monomer which is different from the first, leading to a block copolymer. Clay can be a natural or synthetic material. When the clay material is synthetic, it can be produced by processes in gas phase or sol-gel, for example Si02, [for example Aerosil® by Degussa; Ludox® by DuPo'nt; Snowtex® from Nissan Chemical; | Bayer's Levasil®; or Silysia® from Fuji Silysia Chemical]; colloidal silica [for example Klebosol®], or organosols [for example Highlink® OG by Clariant]. Typical clays are natural or synthetic phyllosilicates, which can be organophilically modified montmorillonites [for example Nanomer® from Nanocor or Nanofil® from Suedchemie], bentonites [for example Cloisite® from Southern Clay Products], beidelites, hectorites, saponites, 'ntronitas, sauconitas, vermiculitas, lediquitas, magadiitas, keniaitas or estevensitas. These materials are commercially available in their natural or partially interspersed form. Special preference is given to a process where the natural or synthetic clay is selected from the group consisting of smectite, phyllosilicate, montmorillonite, saponite, beidelite, montronite, hectorite, stevensite, vermiculite, kaolinite, halosite, synthetic phyllosilicates, and combinations thereof . The most preferred is montmorillonite. Additional aspects of the invention are a nanocomposite dispersion of monomeric / polymeric clay obtainable by a process as described above, a composition comprising an aqueous dispersion of a natural or synthetic clay which is partially interspersed and / or exfoliated and a compound such as a composition was described above, which additionally contains an ethylenically unsaturated monomer and / or an organic solvent. Yet another aspect of the invention is the use of a compound of formula I or II for the polymerization of ethylenically unsaturated monomers and the use of a nanocomposition dispersion of monomeric / polymeric clay obtainable according to the process as defined above as an additive in paints , coatings, inks, adhesives, reactive diluents or in thermoplastic materials. The following examples illustrate the invention.
A) Examples of Preparation of the Compounds Example Al: Chloride of. { 4- [1- (4-tert-butyl-2, 2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy) -ethyl] -benzyl} -triethylammonium (compound 101, Table 1) a) l-tert-butyl-4- [1- (4-chloromethyl-phenyl) -ethoxy] -3,3-diethyl-5,5-dimethyl-piperazin-2 -one To a solution of 13.4 g (0.052 mol) of 1-tert-butyl-3, 3-diethyl-5, 5-dimethyl-piperazin-2-on-4-N-oxy (prepared according to Ger. (DE 19949352 Al) and 8 g (0.052 mole) of 4-chloromethylstyrene in 320 ml of ethanol were added with 5 g (0.00788 mole) of (S, S) -Jacobsen catalyst, then 9.6 ml ( 0.052 mol) of t-butyl hydroperoxide (70% in H20) followed by 4 g (0.010 mol) of sodium borohydride The mixture was stirred at room temperature under argon for 20 h and then evaporated under vacuum. with 50 ml of water and then extracted with 2x50 ml of dichloromethane.The extract was dried over MgSO4 and purified by chromatography on silica gel (hexane-ethyl acetate 12: 1). pentane 4.5 g of the title compound were obtained ulo, mp 66-68 ° C. C23H37C1 202 (409.02) calculated: C: 67.54%, H 9.12%, N 6.85; found: C 67.58%, H 9.16%, N 6.77%. b) Quaternization To a solution of 20 ml of triethylamine in 20 ml of acetonitrile was added 4 g (0.0098 mol) of the product obtained under a). The solution was stirred for 10 h at 60 ° C and evaporated. The solid residue was suspended in 30 ml of t-butyl methyl ether, filtered and dried. 4.7 g of the title compound were obtained as a white powder. | "" H-NMR (300 MHz, CDC13): 7.57-7.49 m (2ArH), 7.41-7.38 m (2 ArH), 4.93-4.69 m (3H), 3.57-3.37 m (6 H), 3.21-2.93 m (2H), 2.0-0.62 (37 H).
Example A2: 4- iodide. { 4- [1- (4-tert-butyl-2, 2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy) -ethyl] -benzoyl} -1,1-dimethyl-piperazin-l-io (compound 102, Table 1) a) l-tert-butyl-3, 3-diethyl-5,5-dimethyl-4-. { 1- [4- (4-methyl-piperazin-1-carbonyl) -phenyl] -ethoxy} -piperacin-2-one To a solution of 0.5 g (0.00124 mol) of 4- [1- (4-tert-butyl-2, 2-diethyl-6,6-dimethyl-3-oxo-piperazine- 1-yloxy) -ethyl] -benzoic acid (prepared according to O 01/02345 A2) in 10 ml of dichloromethane was added 0.4 g (0.00248 mol) of carbonyldiimidazole. The mixture was stirred for 30 minutes under argon at room temperature. Subsequently, 0.275 ml (0.00248 mol) of N-methylpiperazine was added and the solution was stirred for 12 h in addition. The solution was then washed with 3 x with 5 ml of water, dried over MgSO 4, and evaporated. The residue was purified by chromatography on silica gel (hexane-ethyl acetate 2: 1) and 0.46 g of the title compound was obtained as a viscous oil. 1 H-NMR (300 MHz, CDC13): 7.39-7.28 m (4 ArH), 4.75-4.69 m (1H), 4-0.65 (41H). b) Quaternization To a solution of 1 g (0.002 mol) of the product obtained under a) in 2 ml of acetonitrile was added 2 ml of methyl iodide and the solution was stirred at room temperature for 1 h. After evaporation, 1.2 g of the title compound was obtained as a yellow powder. 1 H-NMR (300 MHz, DMSO-d 6): 7.45 s (4 ArH), 4.79-4.73 m (1H), 4.1-0.58 m (43H).
Example A3: bromide of. { 3- [2- (2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy) -propionylamino] -propyl} -ethyl-dimethyl-ammonium (compound 103, Table 1) a) 2-chloro-N- (3-dimethylamino-propyl) -propionamide To 12.25 g (0.1 mol) of methyl ester of 2-chloropropionic acid were added 10.25 g ( 0.1 mol) of 3-dimethylamino-1-propylamine at such a rate that the reaction temperature remained below 40 ° C. The mixture was stirred for 4 h at room temperature and subsequently evaporated at 40 ° C / 1 mbar. Subsequently, the methanol formed in the reaction was distilled. 18.4 g of the title compound were obtained as a colorless oil. "" "H-NMR (300 MHz, CDC13): 8.47 s broad (NH), 4.41-4.34 C (1H), 3.40-3.34 m (2H), 2.47-2.40 m (2H), 2.24 s (6H), 1.70-1.68 d (3H), 1.73-1.64 ra (2H) b) 2- (2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy) -N- (3-dimethylamino-propyl) -propionamide To a solution of 13.85 g (0.07 mol) of 2, 6-Diethyl-2, 3,6-trimethyl-piperidin-1-N-oxyl (prepared according to Ger. Offen DE 2621841) in 70 ml of ethyl acetate was added 13.9 g (0.14 mol) of Cu (I) chloride. ) under argon followed by 24.25 g (0.14 mol) of pentamethyl diethylenetriamine (PMDETA). Subsequently within 10 minutes, 14.95 g (0.0735 mol) of the product obtained under a) were added per drip. The mixture was stirred at room temperature for 12 h, followed by the addition of an additional 3.05 g of the chloramide prepared under a), 2 g of CuCl and 4.3 ml of PMDETA, 20 ml of ethyl acetate and 10 ml of DMF. The mixture was then stirred for an additional 96 h at room temperature. The suspension was filtered and the filter cake was washed with 100 ml of ethyl acetate. The filtrate was washed with 3 x 100 ml of water, then with 2x60 ml of an aqueous sodium salt solution of 1% EDT7A and dried over MgSO4. The residue was purified by chromatography on silica gel (hexane-ethyl acetate 2: 1). 7.7 g of the title compound were obtained as a thick yellow oil. C2oH41N302 (355.8) found: MH + = 356.3 (APCI-MS). c) Quaternization To a solution of 7.6 g (0.0214 mol) of the product obtained under b) in 10 ml of acetonitrile is added in 10 ml of ethyl bromide and the solution was stirred for 12 h at room temperature. After evaporation, 9 g of the title compound were obtained as a white powder. For [C22H46N3O2] + x Br ~ = [384.64] x [79.904]; found M + (Cation) = 384.6 (ESI-MS by Infusion) Example A4: bromide of. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -propionylamino] -propyl} -ethyl-dimethyl-ammonium (compound 104, Table 1) a) 2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -. N. - (3-dimethylamino-propyl) -propionamide To a solution of 21.4 g (0.1 mol) of 2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-lN-oxyl (prepared according to Ger Offen DE 19909767 Al) in 50 ml of DMF were added 19.8 g (0.2 mol) of Cu (I) chloride under argon. Subsequently, 34.7 g (0.2 mol) of pentamethyl diethylenetriamine (PMDETA) and 22.1 g (0.11 mol) 2-chloro-N- (3-dimethylamino-propyl) -propionamide (prepared according to Example A3) were added within 20 minutes. The temperature during the addition was kept below 40 ° C. The mixture was stirred 4 h at room temperature followed by the addition of 500 ml of water and 150 ml of dichloromethane. The organic phase was separated and the aqueous phase was extracted with 2x100 ml of dichloromethane. The organic phases were washed with 5x100 ml of water, then with 3x60 ml of aqueous sodium salt solution of 1% EDTA, dried over MgSO 4 and evaporated. 33.55 g of the title compound were obtained as a thick yellow oil. 1 H-NMR (300 MHz, CDC13): 7.34-7.14 s broad (1H), 4.29-4.20 m (2H), 3.6-3.1 m (2H), 2.6-0.83 m (30H), 2.22 s (6 b) Quaternization To a solution of 28.35 g (0.076 mol) of the product obtained under a) in 25 ml of acetonitrile was added 25 ml of ethyl bromide and the solution was stirred for 12 h at room temperature. After evaporation, 36.5 g of the title compound was obtained as a white powder. For [C22H46N3O3] + x Br "= [400.626] x [79.904]; found M + (cation) = 400.4 (ESI-MS per Infusion) Example A5: [3- (2- {N-Te. -butyl-. - [1- (diethoxy-phosphoryl) -2,2-dimethyl-propyl] -aminooxy] bromide. propionylamino) -propyl] -ethyl-dimethyl-ammonium (compound 105, Table 1) a) (l- {. tert.-Butyl- [1- (3-dimethylamino-propylcarbamoyl) -ethoxy] - diethyl ester - amino.} -2, 2-dimethyl-propyl) -phosphonic From 5.01 g (0.017 mol) of N- (1, l-dimethylethyl) -N- (1-diethylphosphono-2, 2-dimethylpropyl) -N -oxyl (prepared according to Macromolecules (2000), 33 (4), 1141-1147), 3.35 g (0.034 mol) of CuCl, 5.9 g (0.034 mol) of PMDETA and 3.95 g (0.0196 mol) of 2-chloro -N- (3-dimethylamino-propyl) -propionamide (prepared according to Example A3) in 10 ml of DMF yielded 5.6 g of the title compound as a thick yellow oil by analogy with example A4 (reaction time 19 h ). For C2iH46 305P (451.59) calculated C 55.85%, H 10.27%, N 9.31%; found C 55.09%, H 9.91%, N 8.86%. b) Quaternization To a solution of 4.95 g (0.011 mol) of the product obtained under a) in 23 ml of acetonitrile was added 3.3 ml of ethyl bromide and the solution was stirred for 17 h at room temperature. The suspension was evaporated, the residue suspended in 25 ml of diethyl ether and filtered. 5.45 g of the title compound were obtained as a white powder.
Example A6: bromide of. { 3- [2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-ylidenaminooxy] -propyl} -ethyl-dimethyl-ammonium (Compound 106, Table 1) a) 2,6-Diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-??-γ- (3) -dimethylamino-propyl) -oxime To a suspension of sodium hydride (4.36 g, 0.1 mol, 55% in mineral oil) in DMF (30 ml) ao or dropwise the oxime solution of 2,6-diet '1 - 2, 3, 6-r- 'nei -1- (1-phenyl-ethoxy) -piperidin-4-one (16.6 g, u./5 mol, prepared according to that described in WO 02/100831 Al). The mixture was stirred at 150 ° C at 25 ° C and then 3-dimethylaminopropyl chloride (9.48 g, 0.06 mol) was added over 1 h. The mixture was stirred at room temperature for 18 h, then the DMF was evaporated in vacuo. The residue was dissolved in ethyl acetate (100 ml), washed with water (2x25 ml), dried over MgSO 4 and evaporated. Chromatography on a silica gel column (hexane-ethyl acetate 1: 1) gave 12.55 g of the title compound as a colorless oil. MS (DEP-CI), C 25 H 43 N 3 O 2 (417.64): found 418 (100, [M + H] +). b) Quaternization Ethyl bromide (7.5 ml) was added to a solution of 2,6-diethyl-2,3,6-trimethyl-1- (1-phenyl-ethoxy) -piperidin-4-on-O- (3) -dimethylamino-propyl) -oxime (10.2 g, 0.0244 mol) in acetonitrile (12 ml). The solution was stirred 24 h at room temperature and then evaporated. The residue was dissolved in dichloromethane, dried over MgSO4 and evaporated to give 11.5g of the title compound as a white powder. EM '(ESI), cation C27H43N3O2 (446.4): found 446. 9.
Ejemp Al: teref to 3 bromide Je. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -propionyl-amino] -propyl} -ethyl-dimethyl-ammonium (Compound 107, Table 1) a) Bis- (2, e-die-bil-2,3,6-trimethyl-piperidin-N-oxyl-4-yl) terephthalic acid ester drip Terephthaloyl chloride (12.2 g, 0.06 mol) to a solution of 2,6-diethyl-2,3,6-trimethyl-plperidin-4-hydroxy-N-oxyl (25.72 g, 0.12 mol, prepared as described in DE 19909767 Al) in dichloromethane (80 ml) and pyridine (30 ml). The mixture was stirred 72 h, then diluted with dichloromethane (100 ml) and water (100 ml). The organic layer was washed with water (2x 50 ml), dried over MgSO 4 and evaporated. The residue was chromatographed on a column of silica gel (500 g, hexanes-ethyl acetate 4: 1) to give 31.85 g of the title compound as a thick red oil. b) bis-. { 1- [1- (3-dimethylamino-propylcarbamoyl) -ethoxy] -2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl} terephthalic acid ester The bis- (2,6-diethyl-2,3,6-trimethyl-piperidin-N-oxyl-4-yl) ester of terephthalic acid (16.76 g, 0.03 mol), CuCl (11.9 g, 0.12) mol), PMDETft (20.8g, 0.12 mol) and 2-chloro-N- (3-dimethylamino-propyl) -propionamide (13.7g, 0.071 mol) were reacted as described in Example A3 to give 21. lg of the composed of the title as an amorphous solid. MS (APCI), C48H84N608 (873.24): found M + = 872.8 c) Quaternization Ethyl bromide (7.5 ml) was added to a bis- solution. { 1- [1- (3-dimethylamino-propylcarbamoyl) -ethoxy] -2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl} terephthalic acid ester (11. Og, 0.0125 mol) in acetonitrile (20 ml). The mixture was stirred at room temperature for 17 h and then evaporated to give 14.1 g of the title compound as a colorless amorphous solid. EM (ESI), cation C52H94N608 (930.7): found 931. 8 Example A8: Ethyl bromide. { 3- [2- (4-hydroxy-2,2,6,6-tetramethyl-piperidin-1-yloxy) -propionylamino] -propyl} -dimethyl-ammonium (Compound 108, Table 1) a) N- (3-Dimethylamino-propyl) -2- (4-hydroxy-2), 2,6,6-tetramethyl-piperidin-1-yloxy) -propionamide 4-hydroxy-TEMPO (25.84 g, 0.15 mol), CuCl (29.7 g, 0.3 mol), PMDETZA (52.0 g, 0.3 mol) were reacted and 2-chloro-N- (3-dimethylamino-propyl) -propionamide (35.75g, 0.18 mol) as described in Example A3. The final purification of the residue after the extraction work was carried out by crystallization of toluene (45 ml) and hexane (50 ml) to give 31.13 g of the title compound as a white solid pf. 85-88 ° C. For C17H35 3O3 (329.49)% calculated /% found: C 61.97 / 61.85, H 10.71 / 10.55, N 12.75 / 12.61. b) Quaternization Ethyl bromide (9.85 ml) was added to a solution of N- (3-dimethylamino-propyl) -2- (-hydroxy-2,2,6,6-tetramethyl-piperidin-1-yloxy) -propionamide (10.9 g, 0.033 mol) in acetonitrile (30 ml). The mixture is stirred at room temperature for 22 h and then evaporated to 14.7 g of the title compound as a colorless amorphous solid. MS (ESI) cation C19H40N3O3 (358.3): found 358.6 Example A9: Bromide of. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -2-methyl-propionylamino] -propyl} -ethyl-dimethyl-ammonium (Compound 109, Table 1) Ethyl bromide (12 ml) was added to a solution of 2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1) -yloxy) -N- (3-dimethylamino-propyl) -2-methyl-propionamide (20.5 g, 0.053 mol, Compound 110) in acetonitrile (35 ml). The mixture was stirred for 18 h at room temperature and then evaporated to give 26.63 g of the title compound as a colorless solid. MS (ESI) cation C23H48 303 (414.4): found 414.5 Example A10: 2- (2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -, N. - (3-dimethylamino-propyl) -2-methyl-propionamide (Compound 110, Table 1) a) 2-Bromo-N- (3-dimethylamino-propyl) -2-methyl-propionamide To a solution of 3-dimethylaminopropylamine ( 25 mL, 0.1 mol) in THF (50 mL) was added dropwise over 50 minutes and while maintaining the temperature between 0-10 ° C, bromoisobutyroyl bromide (23.0 g, 0.1 mol). The mixture was stirred for a further 3 h at room temperature and then the THF was evaporated in vacuo. Water (20 ml) was added to the residue and the mixture was extracted with t-butyl methyl ether (2 x 30 ml) and ethyl acetate (30 ml). The combined extracts were washed with saturated NaCl solution (10 mL), dried over MgSO4 and evaporated to give 24.1 g of the title compound as a colorless oil. 1 H-NMR (300 MHz, CDC13): 8.51 (broad s, MH), 3.39- 3.34 (m, CH2), 2.47-2.43 (t, CH2), 2.25 (s, 2 x CH3), 1.94 (s, 2 x CH3), 1.72-1.64 (m, CH2) b) 2 (2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -H- (3-dimethylamino-propyl) -2-methyl-propionamide Reacted 2, 6 -diethyl-2,3,6-trimethyl-piperidin-4-hydroxy-N-oxyl (12.86 g, 0.06 mol, prepared as described in DE 19909767 Al), CuCl (11.9 g, 0.12 mol), PMDETA (20.8 g, 0.12 mol) and 2-bromo-M- (3-dimethylamino-propyl) -2-methyl-propionamide (16.5 g, 0.066 mol) as described in Example A3 to give 23.6 g of the title compound as a solid. amorphous white aH-NMR (300 MHz, CDCl 3): 7.4-7.25 (broad s, NH), 4.19-4.11 (m, 1H), 3.44-3.24 (m, 2H), 2.39-0.79 (m, 39H).
Example All: Benzyl chloride. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -2-methyl-propionylamino] -propyl-dimethyl-ammonium (Compound 111, Table 1) Benzyl chloride (0.87g, 0.0069 mol) was added to a solution of 2- (2,6-diethyl-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -N- (3-dimethylamino- propyl) -2-methyl-propionamide (2.2 g, 0.0057 mol, Compound 110) in acetonitrile (3 mL). The mixture was stirred for 19 h at room temperature and then evaporated. The residue was triturated with diethyl ether to remove excess benzyl chloride, the solid was filtered and dried to give 3.0 g of the title compound as a colorless amorphous solid. MS (ESI) cation C28H50 3O3 (476.4): found 476.4 Example A12: Benzyl chloride. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -propionylamino] -propyl} dimethyl-ammonium (Compound 112, Table 1) Benzyl chloride (3.8 g, 0.03 mol) was added to a solution of 2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine). 1-yloxy) - N.- (3-diraethylamino-propyl) -propionamide (10.1 g, 0.0272 mol) in acetonitrile (15 ml). The mixture was stirred for 18 h at room temperature and then evaporated. The residue was triturated with diethyl ether to remove excess benzyl chloride, the solid was filtered and dried to give 13.1 g of the title compound as a colorless amorphous solid. ^ H-RM OOO MHz, MeOH-d4): 7.60-7.51 (m, C6H5), 4.56 (s, CH2), 4.25-4.15 (m, 2H), 3.35-3.29 (m, 4H), 3.06 (s, 6H), 2.15-0.80 (m, 29H).
Example A13: Tributyl bromide. { 3- [2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -propionyloxy] -propyl} -phosphonium (Compound 113, Table 1) a) 3-bromo-propyl ester of 2-bromo-propionic acid 3-Bromopropanol (10.75 g, 0.075 mol) was added over 20 minutes to a solution of 2-bromopropionyl bromide (17.9 g). g, 0.079 mol) in toluene (75 ml) maintaining the temperature between 15-20 ° C. The mixture was stirred for 6 h at room temperature and then poured under vigorous stirring into 1M Na 2 CO 3 solution (80 ml). The organic layer was separated, washed with water (3 x 50 mL), dried over MgSO / j and evaporated to give 19.75 g of the title compound as a colorless oil. 1 H-NMR (300 MHz, CDC13): 4.42-4.24 (m, CH + CH 2), 3.55-3.47 (t, CH 2), 2.27-2.19 (m, CH 2), 1.84-1.82 (d, CH 3). b) 2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy) -propionic acid 3-bromo-propyl ester 2,6-diethyl-2-reacted, 3, 6-trimethyl-piperidin-4-hydroxy-N-oxyl (10.7 g, 0.05 mol, prepared as described in DE 19909767 Al), CuCl (9.9 g, 0.1 mol), PMDETA (17.3 g, 0.1 mol) and 2-bromo-propionic acid 3-bromo-propyl ester (17 g, 0.055 mol) as described in Example A3 to give 16.4 g of the title compound as a colorless oil. "" li-NMR (300 MHz, CDC13): 4.38-4.17 (m, 4H), 3.54-3.46 (m, 2H), 2.23-0.79 (m, 28H). c) Quaternization Tributylphosphine (3 ml, 0.012 mol) was added to a solution of 2- (2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidine-3-bromo-propyl ester) iloxy) -propionic (4.08 g, 0.01 mol) in acetoniuril (5 ml). The solution was stirred under argon at 60 ° C for 23 h. The solvent was evaporated and the residue was triturated with diethyl ether (2 x 15 mL) to remove excess phosphine. Drying the oil in insoluble ether, the residue gives 6.45 g of the title compound as a thick resin. 1 H-NMR (300 MHz, CDCl 3): 4.38-4.13 (m, 4H), 2.66-2.47 (m, 8H), 2.1-0.83 (m, 49H). The compounds are summarized from Table 1 Table 1 B) Examples of Application of Polymerization Test Polymerization of n-butyl acrylate with cationic alkoxyamines (ÑOR) Cationic ÑOR were tested in pure n-butyl acrylate monomer: In a 50 ml round bottom flask with vacuum inlet and Nitrogen and magnetic stirrer were mixed 10 g of n-butyl acrylate (BASF, technical quality) with 1.5 mol% of cationic alkoxyamine (OR), it was evacuated and purged with nitrogen three times and polymerized at 140 ° C (Examples B1- B4) in an oil bath for 7-20 h under good agitation. The conversion was measured by 1H-R N, Mn and PDI with GPC in THF, the values are in relation to PS standards. The polymerization results are presented in Table 2 Table 2 OR Time% of Mn PDI Conversion (found) ümsatz% (1H-NMR) Example Bl Compound 101 17 h 90% 6980 1.47 Example B2 Compound 102 20 h 78% 5470 1.24 Example B3 Compound 103 7 h 70% 6660 1.68 Example B4 Compound 104 7 h 60% 5080 1.46 Example B5 7h Compound 106 120 ° C 42% 3770 1.35 7H 140 ° C 94% 6600 1.49 Example B6 22h Compound 107 140 ° C 76% 4000 1.88 Example B7 5h Compound 110 140 ° C 71% 6150 1.21 OR Time% of Mn-PDI Conversion (found) Umsatz% (Hí-NMR) Example B8 7h Compound 111 140 ° C 65% | 6270 1.34 Example B9 7h Compound 112 140 ° C 58% 3680 2.18 The results in Table 2 clearly demonstrate that all compounds are capable of initiating controlled polymerization of n-butyl acrylate.
C) Examples of application of intercalation of silicate laminates with cationic ÑOR Example Cl: Intercalation of (stratified silicate of the Montmorillonite type from Süd Chemie, Germany) with Compound 101. In a 50 ml round bottom flask are dispersed 2.0 g of Nanofilo EXM 588 in 30 ml of a 0.05 solution of Compound 101 in water and stirred with magnetic stirring for 24 h at RT After centrifugation (IEC Centra GP8 Zentrifuge, glass containers of 100-180 ml) with 2000 rpm (corresponding to 850 g) for 20 min, take a sample of the clear supernatant solution, from which the concentration of the remaining compound 101 is determined (= not interleaved ) by UV spectroscopy at 2 = 245 nm. It is determined that the intercalated amount of compound 101 is 358 mg (= 0.702 mmol) for 1 g of layered silicate. The supernatant solution is decanted and the solid washed with water, centrifuged and decanted three times. The procedure is repeated with MeOH. The sedimented, washed product is subjected to pulverized X rays (? = 1.54 Angstrom), giving a main reflection at 2 max = 3.86 °, which corresponds to an interlayer distance d of 2.29 nm. Compared with the native laminated silicate (20max. = 7. Io, = >; d = 1.24 nm) an increase in the interlayer distance of 1.05 nm is obtained, corresponding to approximately the size of the intercalated molecule. The reflection at 2Omax. = 7.1 ° (d = 1.24 nm), corresponding to the distance of the original sheet, has almost completely disappeared. To verify the adsorbed amount of intercalated compound 101, a sample was dried completely in vacuo and the weight loss was determined by thermographic analysis (TGA): heating rate: 10 ° C / min, from room temperature to 600 ° C. The weight loss obtained from 26.3% corresponds very well to the theoretical value of 26.4%. Examples C2-C5 were carried out analogously to Example Cl, the following cationic ÑORs were intercalated in Nanofilo EXM 588: The results are given in Table 3. Table 3 * on the basis of the total weight of the layered silicate composed of OR D) Examples of Application of Polymerization of Laminated Silicates Intercalated with ÑOR Cationic Example DI: In a 50 ml spherical bottom flask with magnetic stirrer and vacuum inlet and nitrogen, 0.5 g of Compound 101 interspersed with an ultrasonic bath were dispersed and homogenized in an ultrasonic bath. Nanofil EXM588 in 9.5 g n-butyl acrylate (BASF, technical grade) and 4.28 g of 2-methoxypropyl acetate. After evacuating and purging 5 times with N2, the mono-mer was polymerized for 9 h at 140 ° C (bath temperature) under vigorous stirring. The conversion of the monomer, determined by 1 H-NMR, is 85%. The dispersion was subjected to centrifugation at 2000 rpm for 60 min and the settled solid was washed with EtOAc and dried. 57 mg were obtained. It was shown using TGA (see example 6: weight loss 25 ° at 600 ° C: 26%, theoretical: 23%) that the solid is Nanofil EXM 588 interleaved pure with Compound 101 and does not contain polymer. The supernatant solution was evaporated and dried. According to the TGA analysis, the composition contains approximately 10% layered silicate and 90% polymer. X-ray analysis of the solid gave only 2T peaks > 10 °, which indicates a complete exfoliation. A sample (150 mg) of this solid was refluxed with 15 ml of 0.1 M LiBr solution in THE1 for 17 h at 65 ° C, to cleave the polymer from the laminated silicate. After filtration, the molar mass (Mn) and PDI were determined by GPC in THF (in relation to PS standards): Mn = 18000, Mw = 38600, PDI = 2.15. The supernatant solution can be centrifuged for many hours (2000 rpm, corresponding to 850 g), without additional sedimentation. Even after diluting 10 times with EtOAC it is stable for months (no sedimentation was observed), which tests the nm size of the particles, indicating a complete exfoliation.
Comparative Example D-Com. The experiment was carried out by analogy with Example 1 using 0.5 g with a, a'-azodiisobutyramidine dihydrochloride intercalated with Nanofil EXM588 in 9.5 g of 'n-butyl acrylate, without additional solvent. Polymerization 3 h at 80 ° C (bath temperature). The dispersion was diluted with 240 ml of toluene and centrifuged 20 min at 2000 rpm. After washing and drying, 0.35 g of a solid was obtained, which corresponds according to the analysis by TGA to a, a'-azodiisobutyramidine dihydrochloride intercalated with Nanofil EXM588 and does not contain polymer. The supernatant solution was completely evaporated and the residue was dissolved in 150 ml of THF. Centrifugation for 1 h at 2000 rpm again gives 50 mg of a, a'-azodiisobutyramidine dihydrochloride intercalated with Nanofil EXM588. After evaporation of all the solvent and drying 24 h at 60 ° C in vacuo, 2.0 g of polymer were obtained with 0.1 g of a, a'-azodiisobutyramidine dihydrochloride intercalated with Nanofil EXM5881 according to the TGA analysis: weight loss from 25 ° to 600 ° C: 97% (calculated: 96.5%). A sample (150 mg) of this solid was refluxed with 15 ml in 0.1M LiBr solution in THF for 17 h at 65 ° C to separate the polymer from the laminated silicate. Subsequently the solution was filtered and the Mn and PDI were determined by GPC in THF (in relation to PS standards): Mn = 658000, Mw = 1360000, PDI = 2.06. The comparison of the example of the invention Di with the comparative example D-Com shows that the exfoliation of the layered silicate using intercalated NO (ex. 1) followed by controlled radical polymerization is much more efficient: first a monomer conversion was obtained much higher (85% compared to 20%); secondly only a small amount of the layered silicate did not exfoliate (11.4% compared to 80% in ex.1), which can be explained by an efficient start in all the layers, and thirdly the polymer formed It has a controlled molecular weight, much lower.
Example D2: By analogy with the DI example, the controlled free-radical polymerization of styrene was used to exfoliate the Nanofil EXM588 laminated silicate, interspersed with the cationic OR compound 104. The exfoliated laminated silicate contains 66% by weight of polystyrene and % by weight of layered silicate according to that measured by the TGA. The bound polystyrene (on the laminated silicate layers) has a molecular weight of Mn = 2050, Mw = 4010 (analysis by GPC).
Example D3: By analogy with the DI example, 10 g of compound 104 interspersed with Nanofil EXM588 (eg 7), 40 g of n-butyl acrylate (BASF, technical grade) and 120 g of 2-methoxypropyl acetate were dispersed. in a 350 ml spherical bottom flask with an ultra-heat mixer for 25 min. After evacuating and purging 5 times with N2, the monomer was polymerized for 18 h at 140 ° C (oil bath temperature: 155 ° C) with mechanical agitation. The monomer conversion, determined by 1 H-NMR, is 33%. The dispersion was diluted with 100 ml of EtOH and subjected to centrifugation at 2000 rpm for 60 min. Two products were obtained, consisting of laminated silicate exfoliated with bound polymer. The settled solid was dispersed in EtOH, centrifuged (1 h at 2000 rpm) and the sedimented product was dried under high vacuum at 90 ° C overnight. 11.4 g of a gray solid were obtained. The weight loss measured by TGA (25 ° to 600 ° C, 10 ° C / min) gives 46% by weight of polymer bound to laminated silicate (54% by weight). To determine the molecular weight of the bound poly (n-butyl acrylate) chains, a sample (150 mg) of this solid was refluxed in 15 ml of 0.1 M LiBr solution in THF for 17 h at 65 ° C. The GPC gives a molar mass Mn of 3380 and Mw = 5150, corresponding to a PDI of 1.52 and therefore the polymerization is well controlled. The supernatant solution was also evaporated and dried: 18.75 g of solid. The weight loss measured by TGA (25 ° to 600 ° C, 10 ° C / min) gives 60% by weight of polymer bound to laminated silicate (40% by weight). The determination of the molecular weight of the poly (n-butyl acrylate) chains joined by GPC gives a molar mass Mn of 2340 and Mw = 4140, corresponding to a PDI of 1.77. Also in this fraction, the polymerization is well controlled. X-ray analysis of both samples gives only 2T peaks > 10 °, indicating a complete exfoliation.
Example D4: By analogy with example D3, 7.5 g of compound 111 interspersed with Nanofil EXM588 (ex 9), 40 g of n-butyl acrylate (BASF, technical grade) and 120 g of 2-methoxypropyl acetate were dispersed. in a 350 ml spherical bottom flask with an ultra-heat mixer for 25 min. After evacuating and purging 5 times with 2, the monomer was polymerized for 19 h at 140 ° C (oil bath temperature: 155 ° C) with mechanical agitation. The dispersion was placed on a rotary evaporator and all solvents were removed. The highly viscous solid was then cooled in a Soxhlet extraction apparatus and extracted continuously with 300 ml of EtOAc for 18 h. The remaining solid was dried at high vacuum at 90 ° C overnight: 15.5 g of a gray solid was obtained. The weight loss measured by TGA (25 ° to 600 ° C, 10 ° C / min) gives 64% by weight of polymer bound to the laminated silicate (36% by weight). The determination of the molecular weight of the poly (n-butyl acrylate) chains bound by GPC gives a molar mass Mn of 2530 and Mw = 4090, corresponding to a PDI of 1.62, indicating a well-controlled polymerization. The extracted fraction (7.1 g) contained 86% by weight of polymer and 14% by weight of laminated silicate (analysis by TGA) and a molecular weight for the attached poly (n-butyl acrylate) chains of Mn of 2470 and Mw. = 4070 (PDI = 1.65). In both fractions the polymerization is well controlled and the laminated silicate is completely exfoliated (X-ray analysis).
Example D5: By analogy with example D, 7.5 g were dispersed with compound 111 interspersed with Nanofil EXM588 (ex 9), 32.5 g of styrene (Fluka, purum) and 75 g of butyl acetate (Fluka, purum) in a 350 ml spherical bottom flask with an ultra-heat mixer for 25 min. After evacuating and purging 5 times with N2, the monomer was polymerized for 24 h at 120 ° C with mechanical agitation. The dispersion was precipitated in EtOH and the solid was dried in a vacuum oven at 50 ° C overnight: 20 g of white solid. They were ground to a fine powder and placed in a Soxhlet extraction apparatus and extracted continuously with 300 ml of EtOAc for 18 h. The remaining solid was dried at high vacuum at 90 ° C overnight: 12.1 g of a gray solid were obtained. The X-ray analysis shows a complete exfoliation. The weight loss measured by TGA (25 ° to 600 ° C, 10cC / min) gives 72% by weight of polymer bound to the laminated silicate (28% by weight). The determination of the molecular weight of the poly (n-butyl acrylate) chains bound by GPC gives a molar mass Mn of 4190 and Mw = 4640, corresponding to a PDI of 1.11, indicating an extremely good controlled polymerization. The extracted fraction is only 1.6 g, consisting of 82% polystyrene and only 18% laminated silicate, as measured by TGA. This fraction contains mainly well-controlled polystyrene (Mn = 3500, w = 4230, PDI = 1.21) which is not bound to the silicate layers. It was not used for test purposes, üthe total mass balance, it can be calculated that the styrene conversion of 31%. Example D6. : By analogy with example D4, 5 g were dispersed with compound 111 interspersed with Optigel SH, 25.8"g of n-butyl acrylate (BASF, technical grade) and 77.3 g of 2-methoxypropyl acetate (Fluka, purum) in a 350 ml spherical bottom flask in an ultra-heat mixer for 25 min After evacuation and purging 5 times with N2, the monomer is polymerized for 19 h at 140 ° C with mechanical stirring.The dispersion is placed on a rotary evaporator and all the solvents are evaporated, the paste is then placed in a Soxhlet extraction apparatus and extracted continuously with 300 ml of EtOAc for 18 'H. The remaining solid is dried in a high vacuum at 90 ° C overnight: 6.4 are obtained g of a white solid X-ray analysis shows complete exfoliation The weight loss measured by TGA (25 ° to 600 ° C, 10 ° C / min) gives 49% by weight of polymer bound to the laminated silicate (51 % by weight) The determination of the molecular weight of the chains d poly (n-butyl acrylate) joined by GPC gives a molar mass Mn of 3270 and Mw = 5140, corresponding to a PDI of 1.57, indicating a well controlled polymerization. The extracted fraction (5.2 g) consisting of almost pure polymer, not bonded to the laminated silicate layers. From the mass balance, it can be calculated that the conversion of n-butyl acrylate is 32%, leading a theoretical molecular weight (= calculated) of the poly (n-butyl acrylate) chains of Mn = 3270. This perfectly matches the observed molecular weight and again corroborates the perfect control of the length of the polymer chain by this method.

Claims (1)

  1. CLAIMS 1. A compound of formula (I) or (II) characterized in that Gi and G2 independently represent a tertiary carbon atom to which unsubstituted Ci-Ci8 or phenyl alkyl groups or alkyl or phenyl substituted by CN, CO Ci-C18 alkyl, CO-phenyl, C00 alkyl of Ci- are attached. Ci8, O Ci-C18 alkyl, NO2, NH Ci-Ci8 alkyl or N (Ci-Ci8) 2 alkyl or one of Gi and G2 is a secondary carbon atom which is a group -P (0) ( OR22) 2 and the other is as defined above; oiy G2 together with the nitrogen atom to which they are attached form a 5- to 8-membered heterocyclic ring or a polycyclic or spirocyclic 5- to 20-membered heterocyclic ring system, which is substituted with 4 C1-C4 alkyl groups or 2 spirocycloalkyl groups of C5-Ci2 in position ortho to the nitrogen atom and which can be further substituted with one or more CI-CIB alkyl groups, Ci-Cia alkoxy or = 0; and which may be interrupted by an additional oxygen or nitrogen atom; with the proviso that at least one of the 4 C 1 -C 4 alkyl groups in the ortho position to the nitrogen atom is an alkyl higher than methyl; Li, L.2 and L4 is a linking group selected from the group consisting of a direct bond, Ri-Y or R2-C (0) -Y- where Y is linked to Gi and / or G2; C1-C25 alkylene, C2-C25 alkylene interrupted by -0-, -S-, -SO-, -SO? -, \ -R3, ° Q- I 0 O C-O -C- - phenylene and C5-C8 cycloalkylene; Y is 0, or NR9 L3 is a group containing at least one carbon atom and therefore the radical · 1 ^ - (? 5+? ") Derived from the group which is capable of initiating the polymerization of ethylenically unsaturated monomers; Q2 is a direct link, 0, NR5 or NR5R6; Q + is a cationic group selected from the group consisting of where Ri is Ci-Cie alkylene, R2 is a Ci-Cig direct bond or alkylene, R3 is hydrogen or Ci-Ci3 alkyl, R4 is hydrogen or Ci-Ctg alkyl, R5, Re and 7 are each independently hydrogen, Ci-Ci8 alkyl, C3-C12 cycloalkyl, C7-C9 phenyl or phenylalkyl or C6-Ci0 heteroaryl which may or may not be substituted by halogen, OH, N02, CN, Ci-C alkoxy , or R5, 6 and R7 together with the nitrogen or phosphorus atom to which they are attached form a monocyclic or polycyclic ring of 3-12 members, which may contain additional heteroatoms; R8 is hydrogen or C1-C25 alkyl, C3-C25 alkyl interrupted by oxygen, sulfur or by -R; o / 3 C2-C24 alkenyl, R9 is hydrogen, CJ-CIB alkyl, C3-Cig alkenyl, C3-Ci8 alkynyl, phenyl, C7-C9 phenylalkyl, which may or may not be substituted by one or more hydroxy, halogen or C1-6 alkoxy groups C4; R22 is Ci-Ci8 alkyl; X "is the anion of a Ci-Ci8 carboxylic acid which may contain more than one group of carboxylic acid, fluorine, chlorine, bromine, iodine, nitrite, nitrate, hydroxide, ate, sulfate acid, sulfate, alkoxy sulfate, Ci-Cj.8, aromatic or aliphatic sulfonate, carbonate, acid carbonate, perchlorate, chlorate, tetrafluoroborate, borate, phosphate, acid phosphate, diacid phosphate or mixtures thereof, and p, q, and r are independently a different number from each other. 0 to 10 and at least one is different from 0. 2. The compound according to claim 1, characterized in that in formula I or II -LT (Q + X "), -L2 (Q + X-), and -L3 (Q + X "), are a group characterized in that Ki and K2 are hydrogen, Ci-Ci8 alkyl, C5-C12 cycloalkyl, phenyl or phenylalkyl of C7-C9 and K3 is a group -COK4 or where K4 is -y - [(CH2-CH2) - (CH2) s-N + R5R6 X ~] t -CH2-CH2- (CH2) s ~ N + R5R6R7 X ~ O -Y-CH2-CHOH-CH2-N + R5R6X "" -. { [(CH2-CH2) - (CH2) 3-N + X "R5R6] t-CH2-CH2- (CH2) S-N + R5R6R7 X ~.} U, where s is a number from 0 to 8, t is a number from 0 to 4 and u is 0 or 1 and Y is -O- or -NR9; X Z is -C (0) - or a direct bond, if Z is -C (0) -, K5 has the same meaning as ¾, if Z is a direct bond, K3 is Y-CH2-CHOH-CH2-N " i R5R6 X "- {t (CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2- (CH2) S- + R5R6R7 -} OR, Q + X ~, -CH2Q + X "or -CHCH3Q + X"; and Y is -0- or -NRQ or a direct link; the other substituents are as defined in claim 1. 3. The compound according to claim 1 of the formulas la, Ib, Ic, Id or (la) (Ib) (le) (le) (Id) characterized in that Qi is a direct bond or a group -C¾-; if Qi is a direct bond, T8 is hydrogen, if Qi is -CH2-, Tg is methyl or ethyl; Ti, T2, T3 and are independently methyl or ethyl with the proviso that at least one is ethyl; T7 and I are independently hydrogen or methyl; T5 y- T6 are hydrogen or 5 and? 6 together are a group = 0, = N0H, = N0-T9 or T5 is hydrogen and T6 is -0-T9 or -NR9-T9 where T9 is hydrogen, R9 or -C (0) -R9, wherein R9 is hydrogen, Ci-C18 alkyl, C3-C18 alkenyl, C3-Ci8 alkynyl, phenyl, C7-Cg phenylalkyl, which may or may not be substituted by one or more hydroxy groups , halogen or Ci-C4 alkoxy; Tu, T12, T13, 14, 15 and Ti6 are independently Ci-Ci8 alkyl, C3-C18 alkenyl, C3-C18 alkynyl, C5-C12 cycloalkyl, phenyl or C7-Cg phenylalkyl; or T is hydrogen and 12 is a group -P (0) (OC2H5) 2 and the others are as defined above; or u and T14 are a group - CH2-O-T9 and the others are as defined above; or Ti6 is a group -C (0) -Y-Rs and the others are as defined above; or Tu, T 12 and T13 are a group -CH20H; -L3 (Q + X), is a group where Ki and K2 are hydrogen, C5-C12 cycloalkyl, phenyl or phenylalkyl of C7-C9 and ¾ is a group -COK4 or where K4 is Y - [(CH2-CH2) - (CH2) S-N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 X" or -Y-CH2-CHOH-CH2-N + R5R6X " - { [(CH2-CH2) - (CH2) s-N + X ~ R5R6] t ~ CH2-CH2- (CH2) S-N + R5R6R7 X "} u, where s and t is a number from 0 to 4 and u is 0 or l; or is a group R5 -N N X Z is -C (O) - or a direct bond, if Z is -C (O) - K5 has the meaning of K4, if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X_- . { [(CH2-CH2) - (CH2) S-N + R5R6 X ~] t -CH2-CH2- (CH2) s-N + R5ReR7X ~} u, Q '"X", -CH2Q + X ~ or -CHCH3Q + X ~; And it is -O- or -NR9; X "and the other substituents are as defined in claim 1. The compound according to claim 1 of formula lia, Ilb, lie, lid or lie. characterized in that Ai and A2 are independently hydrogen or together with the carbon atom to which they are attached form a carbonyl group, ~ C (0) -; D is a direct bond or C1-C12 alkylene, C1-C12 alkylene which is interrupted by one or more 0, S, or NR9 atoms, C5-Cj.2 cycloalkylene, or phenylene; E is a group -NR9- (CH2) X-NR9- where x is a number from 2 to 12 or a group v is a number from 0 to 10 and w is 0 or 1; Qi is a direct link or a group -CH2-; if Qx is a direct link, T8 is hydrogen, if Qi is -C¾ > -, s is hydrogen, methyl or ethyl; And it is -0- or -NR9; Ti, T2, T3 and Ti are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; -L3 (Q + X ~), is a group where Ki and K2 are hydrogen, C5-C12 cycloalkyl, phenyl or phenylalkyl of C7-Cg and K3 is a group -COK4 or. < ^^ > -Z-K where · K4 is Y- [(CH2-CH2) - (CH2) S-N + R5R5 X "] t-CH2-CH2- (CH2) s-l <" R5R6R7 X or -Y-CH2-CHOH-CH2- + R5R6X_-. { [(CH2-CH2) - (CH2) S-N + R5R6 X "] t -CH2-CH2- (CH2) s-N + R5ReR7 X" '} u, where s and t is a number from 0 to 4 and u is 0 or 1; or X - S X Z is -C (0) - or a direct bond, if Z is -C (0) - K5 has the meaning of K4r if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2- (CH2) S- + R5R6R7X_} or, Q + X ~, -CH2Q + X ~ or -CHCH3Q + X "; X and the other substituents are as defined in claim 1. 5. A compound according to claim 1 of formula Illa, Illb, lile, Illd or lile. (Illa) (lllb) (lile) K6-ON N- [CH2CH2 (CH2) VO-] W-K7 (Illd) (lile) Ti, T2, T3 and? 4 are independently methyl or ethyl with the proviso that at minus one is ethyl; ?? it is hydrogen or methyl; And it is 0 or NRg; Qi is a direct link or a group -C¾-; if Qi is a direct bond, T8 is hydrogen, if Ch is -CH2-, T8 is methyl or ethyl; v is a number from 0 to 10 and w is 0 or 1; K7 is a group -CH2-CHOH-CH2-N + R5R6 X ~ -. { [(CH2-CH2) - (CH2) S-N + R5R6 X-] t-CH2-CH2- (CH2) s- + R5R6R7 X ".}. U, where syt is a number from 0 to 4 and u is 0 or 1, or a group -Di- Q + X "where ?? is Ci-Ci2 alkylene, Ci-Ci2 alkylene which is interrupted by one or more 0, S, or NRg atoms, C5-Ci2 cycloalkylene or phenylene; K6 is selected from the group consisting of -CH2-aryl, (C18 alkyl) -C-aryl f -CH2-CH2-aryl, (C5-C6 cycloalkyl) 2CCN, (Ci-C ^^ CCN alkyl, -CH2CH = CH2, (C1-C12) alkyl -CR30-C (O) -alkyl (Ci-C12), alkyl (from Ci-C12) -CR30-C (O) -aryl (from Ce-Cio), alkyl (from C1-C12) -CR30-C (O) -alkoxy (from C1-C12), alkyl (from C1-C12) -CR30-C (O) -phenoxy, alkyl (of Ci-C12) -CR30-C (O) -N-dialkyl (of C1-C12) r alkyl (of C1-C12) -CR30-CO-NH alkyl ( of C1-C12), alkyl of (of C1-C12) -CR30-CO-NH2, -CH2CH = CH-CH3, -CH2-C (CH3) = CH2, ^ Q | _J -CH2-CH = CH-phe, _Q | _ | _? ^, 3-cyclohexe '2 3 and R3o is hydrogen or Ci-C] _2 alkyl; the alkyl groups are substituted or not with one or more -OH, -COOH or -C (O) R30 groups; and the aryl groups are pheor naphthyl which are substituted or unsubstituted with C1-C12 alkyl, halogen, Ci-Ci2 alkoxy, C1-C12 alkylcarbo glycidyloxy, OH, -COOH or -C00 alkyl (C1-C12) ) and X "and the other substituents are as defined in claim 1. 6. The compound according to the formula IVa where Ti, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; Ei is where x is a number from 2 to 12; K6 is selected from the group consisting of -CH2-CH2-aryl, l of C5-C6) 2CCN, (C 1 -C 12 alkyl) 2CCN, -CH 2 CH = CH 2, (C 1 -C 12 alkyl) -CR 30 -C (O) -alkyl (Ci-C 12), alkyl (Ci-C 12) -CR 30 -C (O ) -aryl (from Ce-Cio), alkyl (from Ci-Ci2) -CR20-C (O) -alkoxy (from C1-C12), alkyl (from C1-C12) -CR30-C (O) -phenoxy, alkyl (of C1-C12) -CR30-C (0) -N-dialkyl (of C1-C12), alkyl (of Ci-C12) -CR30-CO-NH alkyl (of Ci-Ci2), alkyl (de? ? -? ^) -CR30-CO-NH2, -CH2CH = CH-CH3, -CH2- C (CH3) = CH2, ^ CH-CH2-CH = CH-phe _Q (_ | _Q-2-, 3-cyclohexe R30 is hydrogen or C1-C12 alkyl; the alkyl groups are substituted or not with one or more -OH, -COOH or -C (O) R30 groups; and the aryl groups are pheor naphthyl which are unsubstituted or substituted by C -C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylcarbo glycidyloxy, OH, -COOH or -C00 alkyl (from Ci-C12) ) and X ~ and the other substituents are as defined in claim 1. 7. The compound according to claim 1 of formula Va, Vb, Ve, Vd or Ve (Go) (Vb) (Go) (Vd) (Go) characterized in that?, T2, T3 and T4 are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; Qi is a direct link or a group -CH2-; if Qi is a direct bond, T8 is hydrogen, if Qi is -CH2-, T3 is methyl or ethyl; Kj and K2 are hydrogen, C5-C12 cycloalkyl, pheor phelkyl of C7-C9 and K3 is a group -C0K4 or where K4 is Y- [(CH2-CH2) - (CH2) S-N + R5R6 X "] t-CH2-CH2- (CH2) S ~ N + R5R6R7"or -y-CH2-CHOH-CH2-N + R5R6X_- { [(CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2- (CH2) S-N + R5R6R7 X ~} u, where s and t is a number from 0 to 4 and u is 0 or l; or Z is -C (0) - or a direct bond, if Z is -C (0) - K5 has the meaning of K,. if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6-t-CH2-CH2- (CH2) S-N + R5R6 7 X"} u, Q + X ", 'CH2Q + X ~ or -CHCH3Q + X'; K7 is a group -CH2-CH0H-CH2-N + R5R6 X" -. { [(CH2-CH2) - (CH2) S-N + R5R6 X "] t-CH2-CH2- (CH2) S-N + R5R6R7 X ~.} U, where syt is a number from 0 to 4 and u is 0 or 1, or a group - ?? - Q + X "where Di is Ci-C12 alkylene, C-L-CI2 alkylene which is interrupted by one or more 0, S, or NR9 atoms, C5-cycloalkylene Ci2 or phene; X ~ and the other substituents are as defined in claim 1. 8. The compound according to claim 1 of formula Via characterized in that Ti, T2, T3 and a are independently methyl or ethyl with the proviso that at least one is ethyl; T7 is hydrogen or methyl; i and K2 are hydrogen, C5-C12 cycloalkyl, pheor phelkyl of C7-Cg and K3 is a group where K4 is Y- [(CH2-CH2) - (CH2) S-N + R5R6 X "] t-CH2-CH2- (CH2) s R5R6R7 X "or -Y-CH2-CHOH ~ CH2-N + R5R6X" -. { [(CH2-CH2) - (CH2) S- ÷ R5R5 X "] t-CH2-CH2- (CH2) 3-N + R5R6R7 X ~.} U, where syt is a number from 0 to 4 and u is 0 or 1; or Z is -C (O) - or a direct bond, if Z is -C (0) - K5 has the meaning of K4, if Z is a direct bond, K5 is 0-CH2-CHOH-CH2-N + R5R6 X "- { [(CH2-CH2) - (CH2) S-N + R5R6 X"] t-CH2-CH2 ~ (CH2) S "N + R5R6R7 X" } u, Q + X ~ / -CH2Q + X "or -CHCH3Q + X" and X ~ and the other substituents are as defined in claim 1. 9. The compound according to claim 3 of formula Ial, Ibl, Icl, Idl or I read (I read) (Id1) characterized in that Qi is a direct bond or CH2; Ti, T3 are ethyl and T2, T¿ | they are methyl; T7 is methyl or H; if Qi is a direct link, T8 is H; if Qi is CHz r T8 it is methyl or ethyl; Uncle is H if T7 is methyl or Uncle is methyl if T7 is H; u, 12, i3, Ta4, i5 and T16 are independently methyl or ethyl; or T12 is isopropyl,? 13 is phenyl, i4, i5, i6 are methyl; or u is H, T12 is - P (= 0) (OC2H5) 2, Ti 3 is t-butyl and Ti4, T15 Ti6 is methyl; or Tu and T14 are -CH20-T9 and T12, Ti5 are methyl or phenyl and T13, ?? 6 are methyl or ethyl; o Tu, T12, T13, T14, 15 are methyl and T16 is a group -CÓ-O-Rg or -CON (R9) 2; or Tu, 12 and T13 are -CH2OH, T1A is H, T15 is isopropyl and Ti6 phenyl; T9 is hydrogen, R9 or -C (0) ~ Rs, where R9 is hydrogen, Ci-Cia alkyl, C3-Ci8 alkenyl, C3-C18 alkynyl, phenyl, C7-C9 phenylalkyl; i is H, K2 is methyl or ethyl and K3 is a group K4 is -Y-CH2-CH2- (CH2) S-N + X "R5R6R7 or; -Y-CH2-CHOH-CH2-N-CH2-CH2- (CH2) S-N + X" R5R6R7 where Y is O or NR9 and s is a number from 0 to 2; if K3 is Z is -C0- or a direct link; if Z is -CO-, K5 has the same meaning as ¾; if Z is a direct bond, K5 is a group -0-CH2-CHOH-CH2-N-CH2-CH2- (CH2) 3-N + X ~ R5R6R7 or -CH2N + R5R6R7 X "and X ~ and the other substituents they are as defined above 10. The compound according to claim 4 of formula Ilal, Ubi, IIcl or Ildl characterized in that Qi is a direct bond or CH2; Ti, T3 are ethyl and T2, T4 and T7 are methyl; if Qx is a direct link, T8 is H; if Qi is CH2, T8 is methyl or ethyl; D is a direct bond, C1-C12 alkylene or phenylene; E is -NR5- (CH2) X -NR5- where x is from 2 to 12 or a group R9? ·? where Y is = NR9 -And N Y- Ki is H, K2 is methyl or ethyl and K3 is a group -CO-K4 or 'K4 is -Y-CH2-CH2- (CH2) S-N + X "R5R6R7 or; -Y-CH2-CHOH-CH2-N-CH2-CH2- (CH2) S -N + X_R5R6R7 where Y is 0 or NR9 and s is a number from 0 to 2, Rg is hydrogen, Cx to C18 alkyl, C3 to C2 alkenyl, C3 alkynyl to Ci, phenyl, phenyl to C7 to C9. if K3 is ^ ^ 2-K5 '2 is -C0- or a direct bond; if Z is -C0- K5 has the same meaning as 4; if Z is a direct bond K5 is a group -0-CH2-CHOH-CH2-N-CH2-CH2- (CH2) S-N + X ~ R5R6R7 and X ~ and the other substituents are as defined in claim 1 . 11. A process for preparing a nano'composite dispersion of monomeric / polymeric clay, characterized in that it comprises the steps of A) Providing a first aqueous dispersion of a natural or synthetic clay that can be interspersed and / or partially exfoliated and where the clay has a cation interchangeable; adding a compound according to claim 1 to the dispersion and exchanging the cation at least partially; B) Add the dispersion to at least one ethylenically unsaturated monomer and polymerize at least a portion of the ethylenically unsaturated monomer. 12. The process according to claim 11, characterized in that the aqueous phase of step A) is removed at least partially before carrying out step B). 13. The process according to claim 11, characterized in that the compound according to claim 1 is added in an amount of 1% to 100% by weight, based on the weight of the clay. The process according to claim 11, characterized in that the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinyl imidazole, maleic anhydride, (alkyl) acrylic acid anhydrides, salts of (alkyl) acrylic acid, (alkyl) acrylic esters, (meth) acrylonitriles, (alkyl) ) acrylamides, vinyl halides or vinylidene halides or mixtures thereof. 15. The process according to claim 14, characterized in that the ethylenically unsaturated monomers are styrene, a-methyl styrene, p-methyl styrene or a compound of formula CH2 = C (Ra) - (C = Z) -Rb, where Ra is hydrogen or C1-C4 alkyl, Rb is NH2, 0 ~ (Me +), glycidyl, unsubstituted Ci-Ci8 alkoxy, C2-C10 alkoxy interrupted by at least one N and / or 0 atom, or Cx-Ci8 alkoxy substituted with hydroxy, unsubstituted Ci-C18 alkylamino, di (Ci-Cie alkyl) amino, Ci-Cia alkylamino substituted with hydroxy or di (Ci-Cxs alkyl) amino substituted with hydroxy, - 0-CH2-CH2-N (CH3) 2 or -0-CH2-CH2-N + H (CH3) 2 Arf; An ~ is an anion of a monovalent organic or inorganic acid; I am a monovalent metal atom or the ammonium ion. Z is oxygen or sulfur. 16. The process according to claim 11, characterized in that an acid is added which "contains unsaturated monomer, which is selected from the group consisting of methacrylic anhydride, maleic anhydride, itaconic anhydride, acrylic acid, methacrylic acid, itaconic acid, acid maleic, fumaric acid, acryloxypropionic acid, (meth) acryloxy propionic acid, styrene sulfonic acid, ethylene methacrylate-2-sulphonic acid, 2-acrylamido-2-methylpropane, sulfonic acid, phosphoethyl methacrylate, the corresponding salts of the acid-containing monomer , and combinations thereof 17. The process according to claim 11, characterized in that step B) is repeated with a second ethylenically unsaturated monomer which is different from the first, leading to a block copolymer. according to claim 11, characterized in that the natural or synthetic clay is selected from the group. or consisting of smectite, phyllosilicate, montmorillonite, saponite, beidelite, montronite, hectorite, estevensite, vermiculite, kaolinite, halosite, synthetic phyllosilicates, and combinations thereof. 19. A dispersion in a monomeric / polymeric clay nanocomposite characterized in that it is obtained by a process according to claim 11. 20. A composition, characterized in that it comprises an aqueous dispersion of a natural or synthetic clay which is partially interspersed and / or exfoliated and a compound according to claim 1. 21. The composition according to claim 26, characterized in that it additionally contains an ethylenically unsaturated monomer and / or an organic solvent. 22. The use of a compound of formula I or II for the polymerization of ethylenically unsaturated monomers. 23. The use of a dispersion of a monomeric / polymer clay nanocomposite obtained in accordance with claim 11 as an additive in paints, coatings, inks, adhesives, reactive diluents or thermoplastic materials.
MXPA04012885A 2002-06-24 2003-06-17 Cationic alkoxyamines and their use in producing nano particles from natural or synthetic clays. MXPA04012885A (en)

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